CN112442352A - Anhydrous modified glycerol-based cross-linking fracturing fluid system and preparation method and application thereof - Google Patents
Anhydrous modified glycerol-based cross-linking fracturing fluid system and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an anhydrous modified glycerol-based cross-linked fracturing fluid system and a preparation method and application thereof, and relates to the technical field of oil and gas well drilling exploitation. The fracturing fluid system provided by the invention comprises the following preparation raw materials in parts by massMaterial preparation: 5-10 parts by mass of 3-acrylamide-2-methylpropanesulfonic acid, 20-60 parts by mass of acryloyloxyethyl trimethyl ammonium chloride, 10-30 parts by mass of dimethyl diallyl ammonium chloride, 2-5 parts by mass of hydroxyl acrylate, 8-13 parts by mass of acrylamide, 20-70 parts by mass of mixed alcohol, 20-40 parts by mass of white oil, 1.5-5.0 parts by mass of span oil, 0.001-0.3 part by mass of a catalyst, 2-4 parts by mass of a reverse phase demulsifier and 0.8-1.6 parts by mass of a cross-linking agent. The fracturing fluid is an anhydrous system, can be used for high-water-sensitivity strata, and greatly reduces the use of water resources and the pollution of flowback fluid; and has excellent high temperature resistance at 144 ℃ for 170s‑1The viscosity is maintained above 300 mPas after shearing for 1 h.
Description
Technical Field
The invention relates to the technical field of oil and gas well drilling exploitation, in particular to an anhydrous modified glycerol-based cross-linked fracturing fluid system and a preparation method and application thereof.
Background
In recent years, along with the adjustment of national energy structures, coal bed gas, which is an important component of unconventional oil gas with huge storage capacity and great influence on environmental protection, is gradually one of key objects for the exploration and development of unconventional oil gas resources in China.
The storage environment, the storage state and the like of the coal bed gas determine that the fracturing construction is an important mode for realizing the rapid yield increase and the effective development of the coal bed gas. At present, the exploitation of unconventional oil and gas reservoirs at home and abroad mainly adopts water-based fracturing fluid, but the unconventional oil and gas reservoirs usually show poor physical properties and are water-sensitive, so that the water-based fracturing fluid is extremely easy to damage the stratum environment; meanwhile, the water-based fracturing fluid consumes a large amount of water resources and generates a large amount of flowback fluid wastewater, and chemical components in the fracturing fluid can cause potential harm to underground water.
Disclosure of Invention
In view of the above, the present invention aims to provide an anhydrous modified glycerol-based cross-linked fracturing fluid system, and a preparation method and an application thereof. The fracturing fluid provided by the invention is an anhydrous system, can be used for high-water-sensitivity stratum, and greatly reduces the use of water resources and the pollution of flowback fluid.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an anhydrous modified glycerol-based cross-linked fracturing fluid system which comprises the following preparation raw materials in percentage by mass:
the mixed alcohol comprises glycerol, ethylene glycol and 1, 4-butanediol, and the mass ratio of the glycerol to the ethylene glycol to the 1, 4-butanediol is 50-60: 20-30: 10-20; the catalyst is potassium persulfate and/or azo catalyst; the cross-linking agent is an organic zirconium cross-linking agent and/or an organic aluminum cross-linking agent.
Preferably, the anhydrous modified glycerol-based cross-linking fracturing fluid system comprises the following preparation raw materials in percentage by mass:
preferably, the hydroxy acrylate is 4-hydroxybutyl acrylate and/or hydroxypropyl acrylate.
Preferably, the azo catalyst is azobisisobutyronitrile and/or azobisisobutyronitrile hydrochloride; the organic zirconium cross-linking agent is one or more of zirconium isopropoxide, zirconium citrate and zirconium formate; the organic aluminum cross-linking agent is one or more of aluminum acetate, aluminum citrate and aluminum formate.
Preferably, the reverse demulsifier is emulsifier NP-8 and/or emulsifier NP-9.
Preferably, the white oil is D-100 white oil and/or 3# white oil; the span oil is one or more of span 20, span 40 and span 80.
The invention provides a preparation method of an anhydrous modified glycerol-based cross-linked fracturing fluid system, which comprises the following steps:
(1) carrying out first mixing on glycerol, ethylene glycol and 1, 4-butanediol to obtain mixed alcohol;
(2) carrying out second mixing on 2-acrylamide-2-methylpropanesulfonic acid, acryloyloxyethyltrimethyl ammonium chloride, dimethyldiallylammonium chloride, hydroxyl acrylate and acrylamide to obtain a solution A;
carrying out third mixing on the white oil and the span oil to obtain a solution B;
adding the solution A into the solution B for fourth mixing to obtain a pre-emulsion; under the protection of nitrogen, mixing the pre-emulsion with a catalyst for emulsification and homogenization to obtain an emulsion;
heating the emulsion to 87-93 ℃ for polymerization reaction, cooling the obtained reaction liquid to room temperature, and mixing the reaction liquid with a reverse demulsifier to obtain a fracturing fluid thickening agent;
(3) and mixing the mixed alcohol, the fracturing fluid thickening agent and the cross-linking agent to obtain the anhydrous modified glycerol-based cross-linking fracturing fluid system.
Preferably, the time of the polymerization reaction in the step (2) is 4.5-5 h.
Preferably, the cooling in the step (2) is carried out by using cooling water, and the temperature of the cooling water is-15 ℃ to-9 ℃.
The invention provides an application of the anhydrous modified glycerol-based cross-linked fracturing fluid system in the technical scheme or the anhydrous modified glycerol-based cross-linked fracturing fluid system prepared by the preparation method in the technical scheme in the oil and gas exploitation field.
The invention provides an anhydrous modified glycerol-based cross-linked fracturing fluid system which comprises the following preparation raw materials in percentage by mass: 5-10 parts by mass of 3-acrylamide-2-methylpropanesulfonic acid, 20-60 parts by mass of acryloyloxyethyl trimethyl ammonium chloride, 10-30 parts by mass of dimethyl diallyl ammonium chloride, 2-5 parts by mass of hydroxyl acrylate, 8-13 parts by mass of acrylamide, 20-70 parts by mass of mixed alcohol, 20-40 parts by mass of white oil, 1.5-5.0 parts by mass of span oil, 0.001-0.3 part by mass of a catalyst, 2-4 parts by mass of a reverse phase demulsifier and 0.8-1.6 parts by mass of a cross-linking agent; the mixed alcohol comprises glycerol, ethylene glycol and 1, 4-butanediol, and the mass ratio of the glycerol to the ethylene glycol to the 1, 4-butanediol is 50-60: 20-30: 10-20; the catalyst is potassium persulfate and/or azo catalyst;the cross-linking agent is an organic zirconium cross-linking agent and/or an organic aluminum cross-linking agent. The fracturing fluid provided by the invention is an anhydrous system, can be used for high-water-sensitivity stratum, and greatly reduces the use of water resources and the pollution of flowback fluid; the anhydrous modified glycerol-based crosslinking fracturing fluid system provided by the invention has excellent high-temperature resistance, and the temperature is 144 ℃ for 170s-1The viscosity is kept above 300 mPas after shearing for 1h, the industrial application of drilling and exploitation of high water sensitive stratum oil and gas wells can be well met, and the safety is high.
The invention provides a preparation method of the anhydrous modified glycerol-based cross-linking fracturing fluid system, which is simple in process, easy to operate and beneficial to large-scale production.
Drawings
FIG. 1 is a graph of the rheological properties of an anhydrous modified glycerol-based cross-linked fracturing fluid system of example 1;
figure 2 is a graph of the rheological performance of the anhydrous modified glycerol-based cross-linked fracturing fluid system of example 2.
Detailed Description
The invention provides an anhydrous modified glycerol-based cross-linked fracturing fluid system which comprises the following preparation raw materials in percentage by mass:
the mixed alcohol comprises glycerol, ethylene glycol and 1, 4-butanediol, and the mass ratio of the glycerol to the ethylene glycol to the 1, 4-butanediol is 50-60: 20-30: 10-20; the catalyst is potassium persulfate and/or azo catalyst; the cross-linking agent is an organic zirconium cross-linking agent and/or an organic aluminum cross-linking agent.
Unless otherwise specified, all of the materials described in the present invention are commercially available products well known to those skilled in the art.
The raw materials for preparing the anhydrous modified glycerol-based cross-linked fracturing fluid system comprise, by mass, 5-10 parts of 2-acrylamide-2-methylpropanesulfonic acid, preferably 6-8 parts of 2-acrylamide-2-methylpropanesulfonic acid, and more preferably 6.5-7.5 parts of 2-acrylamide-2-methylpropanesulfonic acid. In the invention, the 2-acrylamide-2-methylpropanesulfonic acid plays a temperature resistance role.
The raw materials for preparing the anhydrous modified glycerol-based crosslinking fracturing fluid system comprise, by mass, 20-60 parts of acryloyloxyethyl trimethyl ammonium chloride, preferably 30-50 parts of acryloyloxyethyl trimethyl ammonium chloride, and more preferably 35-45 parts of acryloyloxyethyl trimethyl ammonium chloride. In the invention, the acryloyloxyethyl trimethyl ammonium chloride is a cationic monomer and can promote the molecular weight of the product to be increased in a crosslinking reaction.
The raw materials for preparing the anhydrous modified glycerol-based crosslinking fracturing fluid system comprise, by mass, 10-30 parts of dimethyldiallylammonium chloride, preferably 15-25 parts of dimethyldiallylammonium chloride, and more preferably 18-22 parts of dimethyldiallylammonium chloride. In the invention, the dimethyldiallylammonium chloride is also a cationic monomer and plays a role in promoting crosslinking and dissolution in a fracturing fluid system.
The raw materials for preparing the anhydrous modified glycerol-based cross-linking fracturing fluid system comprise 2-5 parts by mass of hydroxyl acrylate, preferably 3-4 parts by mass, and more preferably 3.5 parts by mass. In the present invention, the hydroxy acrylate is preferably 4-hydroxybutyl acrylate and/or hydroxypropyl acrylate; when the hydroxy acrylate is preferably 4-hydroxybutyl acrylate and hydroxypropyl acrylate, the mixing ratio of the 4-hydroxybutyl acrylate and hydroxypropyl acrylate is not particularly required in the present invention. In the present invention, the hydroxy acrylate functions as a crosslinking agent.
The raw materials for preparing the anhydrous modified glycerol-based cross-linking fracturing fluid system comprise 8-13 parts by mass of acrylamide, preferably 10-12 parts by mass, and more preferably 10.5-11.5 parts by mass. In the present invention, the acrylamide functions as a viscosity increasing agent.
The raw materials for preparing the anhydrous modified glycerol-based cross-linking fracturing fluid system comprise, by mass, 20-70 parts of mixed alcohol, preferably 30-60 parts of mixed alcohol, and more preferably 40-50 parts of mixed alcohol. In the invention, the mixed alcohol comprises glycerol, ethylene glycol and 1, 4-butanediol, and the mass ratio of the glycerol to the ethylene glycol to the 1, 4-butanediol is 50-60: 20-30: 10-20, preferably 55-58: 25-28: 14 to 18, more preferably 57.5: 27.5: 15. in the present invention, the glycerol is preferably 995 food grade glycerol. In the invention, the mixed alcohol is used as a carrier in the fracturing process, is suitable for high-water-sensitivity stratums, and greatly improves the safety.
The raw materials of the anhydrous modified glycerol-based cross-linking fracturing fluid system comprise, by mass, 20-40 parts of white oil, preferably 25-35 parts of white oil, and more preferably 27.5-33.5 parts of white oil. In the present invention, the white oil is preferably D-100 white oil and/or # 3 white oil. In the present invention, the white oil serves as a continuous phase and a dispersion medium.
The raw materials of the anhydrous modified glycerol-based cross-linking fracturing fluid system comprise, by mass, 1.5-5.0 parts of span oil, preferably 2.5-4.0 parts of span oil, and more preferably 2.5-3.5 parts of span oil. In the invention, the span oil is preferably one or more of span 20, span 40 and span 80. In the invention, the span oil is used as an emulsifier and plays a role in emulsifying and homogenizing.
The raw materials for preparing the anhydrous modified glycerol-based crosslinking fracturing fluid system comprise, by mass, 0.001-0.3 part of catalyst, preferably 0.005-0.2 part of catalyst, and more preferably 0.008-0.15 part of catalyst. In the invention, the catalyst is potassium persulfate and/or azo catalyst; when the catalyst is potassium persulfate and an azo catalyst, the mixing proportion of the potassium persulfate and the azo catalyst is not particularly required; the azo catalyst is preferably azobisisobutyronitrile and/or azobisisobutylimidazoline hydrochloride, and when the azo catalyst is preferably azobisisobutyronitrile and azobisisobutylimidazoline hydrochloride, the mixing ratio of the azobisisobutyronitrile and the azobisisobutylimidazoline hydrochloride is not particularly required. In the present invention, the catalyst functions to catalyze the polymerization reaction.
The raw materials for preparing the anhydrous modified glycerol-based cross-linked fracturing fluid system comprise, by mass, 2-4 parts of reverse-phase demulsifier, preferably 2.5-3.5 parts of reverse-phase demulsifier, and more preferably 3 parts of reverse-phase demulsifier. In the present invention, the reverse demulsifier is preferably emulsifier NP-8 and/or emulsifier NP-9; when the reverse demulsifier is preferably emulsifier NP-8 and emulsifier NP-9, the present invention does not particularly require the mixing ratio of emulsifier NP-8 and emulsifier NP-9.
The raw materials for preparing the anhydrous modified glycerol-based crosslinking fracturing fluid system comprise 0.8-1.6 parts by mass of a crosslinking agent, preferably 0.9-1.5 parts by mass, and more preferably 1.0-1.5 parts by mass. In the present invention, the crosslinking agent is an organozirconium-based crosslinking agent and/or an organoaluminum-based crosslinking agent, and when the crosslinking agent is an organozirconium-based crosslinking agent and an organoaluminum-based crosslinking agent, there is no particular requirement on the mixing ratio of the organozirconium-based crosslinking agent and the organoaluminum-based crosslinking agent; the organic zirconium crosslinking agent is preferably one or more of zirconium isopropoxide, zirconium citrate and zirconium formate, and when the organic zirconium crosslinking agent is a mixture of several, the invention has no special requirement on the mixing proportion; the organic aluminum crosslinking agent is preferably one or more of aluminum acetate, aluminum citrate and aluminum formate, and when the organic aluminum crosslinking agent is a mixture of several, the mixing proportion is not particularly required.
In the prior art, the water-based fracturing fluid is difficult to adapt to the requirements of high-water-sensitivity stratum, is difficult to resist high temperature, and generally has no viscosity after being sheared for 1 hour at about 150 ℃; the oil-based fracturing fluid has great potential safety hazard, cannot realize construction safety, and has no operability. The fracturing fluid provided by the invention is an anhydrous system, can be used for high-water-sensitivity stratum, and greatly reduces the use of water resources and the pollution of flowback fluid; the anhydrous modified glycerol-based crosslinking fracturing fluid system provided by the invention has excellent high-temperature resistance, and the temperature is 144 ℃ for 170s-1The viscosity is kept above 300 mPas after shearing for 1h, the industrial application of drilling and exploitation of high water sensitive stratum oil and gas wells can be well met, and the safety is high.
The invention provides a preparation method of an anhydrous modified glycerol-based cross-linked fracturing fluid system, which comprises the following steps:
(1) carrying out first mixing on glycerol, ethylene glycol and 1, 4-butanediol to obtain mixed alcohol;
(2) carrying out second mixing on 2-acrylamide-2-methylpropanesulfonic acid, acryloyloxyethyltrimethyl ammonium chloride, dimethyldiallylammonium chloride, hydroxyl acrylate and acrylamide to obtain a solution A;
carrying out third mixing on the white oil and the span oil to obtain a solution B;
adding the solution A into the solution B for fourth mixing to obtain a pre-emulsion; under the protection of nitrogen, mixing the pre-emulsion with a catalyst for emulsification and homogenization to obtain an emulsion;
heating the emulsion to 87-93 ℃ for polymerization reaction, cooling the obtained reaction liquid to room temperature, and mixing the reaction liquid with a reverse demulsifier to obtain a fracturing fluid thickening agent;
(3) and mixing the mixed alcohol, the fracturing fluid thickening agent and the cross-linking agent to obtain the anhydrous modified glycerol-based cross-linking fracturing fluid system.
The method comprises the steps of mixing glycerol, ethylene glycol and 1, 4-butanediol for the first time to obtain mixed alcohol. The method of the first mixing is not particularly required in the present invention, and the components are uniformly mixed by a mixing method well known to those skilled in the art, specifically, by stirring.
Secondly mixing 2-acrylamide-2-methylpropanesulfonic acid, acryloyloxyethyltrimethyl ammonium chloride, dimethyldiallylammonium chloride, hydroxyl acrylate and acrylamide to obtain a solution A; and carrying out third mixing on the white oil and the span oil to obtain a solution B. The method of the second mixing and the third mixing is not particularly required in the present invention, and the components are uniformly mixed by a mixing method well known to those skilled in the art, specifically, stirring and mixing.
After the solution A and the solution B are obtained, adding the solution A into the solution B for fourth mixing to obtain a pre-emulsion; and mixing the pre-emulsion with a catalyst under the protection of nitrogen, and emulsifying and homogenizing to obtain the emulsion. The method of the fourth mixing method is not particularly required in the present invention, and the mixing can be performed uniformly by a method well known to those skilled in the art, such as stirring and mixing. The emulsifying homogenization is preferably carried out by an emulsifying pump, which is not particularly required by the invention and can be realized by the emulsifying pump well known to the skilled person.
After the emulsion is obtained, the emulsion is heated to 87-93 ℃ for polymerization reaction, and the obtained reaction liquid is cooled to room temperature and then mixed with a reverse demulsifier to obtain the fracturing fluid thickening agent. In the invention, the temperature of the polymerization reaction is preferably 90 ℃, and the time of the polymerization reaction is preferably 4.5-5 h. In the present invention, the cooling is preferably performed using cooling water, and the temperature of the cooling water is preferably-15 ℃ to-9 ℃, and more preferably-12 ℃. The method for mixing the reaction liquid with the reverse demulsifier after cooling to room temperature has no special requirement, and the reaction liquid can be uniformly mixed by adopting a mixing method well known by the technical personnel in the field, such as stirring and mixing.
After the mixed alcohol and the fracturing fluid thickening agent are obtained, the mixed alcohol, the fracturing fluid thickening agent and the crosslinking agent are mixed to obtain the anhydrous modified glycerol-based crosslinking fracturing fluid system. The method for mixing is not particularly required in the present invention, and the mixture can be uniformly mixed by a mixing method known to those skilled in the art, such as stirring and mixing. In the invention, the mixed alcohol, the fracturing fluid thickening agent and the cross-linking agent are mixed and then cross-linked to obtain the anhydrous modified glycerol-based cross-linking fracturing fluid system.
The preparation method of the anhydrous modified glycerol-based cross-linking fracturing fluid system provided by the invention is simple in process, easy to operate and beneficial to large-scale production.
The invention provides an application of the anhydrous modified glycerol-based cross-linked fracturing fluid system in the technical scheme or the anhydrous modified glycerol-based cross-linked fracturing fluid system prepared by the preparation method in the technical scheme in the oil and gas exploitation field. The method of application is not particularly required by the present invention, and may be applied by methods known to those skilled in the art.
The following will describe the anhydrous modified glycerol-based crosslinked fracturing fluid system provided by the present invention, its preparation method and application in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The anhydrous modified glycerol-based cross-linking fracturing fluid system comprises the following preparation raw materials in percentage by mass: 6.5 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid, 35 parts by mass of acryloyloxyethyl trimethyl ammonium chloride, 18.5 parts by mass of dimethyldiallylammonium chloride, 3.5 parts by mass of hydroxyacrylate (4-hydroxybutylacrylate and hydroxypropyl acrylate), 11 parts by mass of acrylamide, 45 parts by mass of mixed alcohol (the mass ratio of glycerol, ethylene glycol and 1, 4-butanediol is 57.5: 27.5: 15), 28 parts by mass of 3# white oil, 3.0 parts by mass of span oil (span 80), 0.0 part by mass of catalysts (potassium persulfate, azobisisobutyronitrile and azobisisobutyronitrile hydrochloride), 3.0 parts by mass of reverse demulsifier (emulsifier NP-9), and 1.0 part by mass of crosslinking agents (zirconium isopropoxide, zirconium citrate, zirconium formate, aluminum acetate, aluminum citrate and aluminum formate). The preparation method comprises the following steps:
(1) carrying out first mixing on glycerol, ethylene glycol and 1, 4-butanediol to obtain mixed alcohol;
(2) 2-acrylamide-2-methylpropanesulfonic acid, acryloyloxyethyltrimethyl ammonium chloride, dimethyldiallylammonium chloride, hydroxyl acrylate and acrylamide are subjected to second mixing and are uniformly stirred to form a solution A;
mixing the white oil and the span oil for the third time, and stirring uniformly to form a solution B;
pouring the solution A into the solution B for fourth mixing, and uniformly stirring to obtain a pre-emulsion; under the protection of nitrogen, adding a catalyst into the pre-emulsion, and simultaneously starting an emulsification pump to emulsify and homogenize to obtain an emulsion; slowly heating the emulsion to 90 +/-3 ℃, continuously reacting and curing for 4.5h, stopping heating, cooling the obtained reaction liquid to room temperature by using cold water at the temperature of-12 +/-3 ℃, adding a reverse demulsifier, and uniformly stirring to obtain a fracturing fluid thickening agent;
(3) and (3) adding the fracturing fluid thickening agent and the cross-linking agent in the step (2) into the mixed alcohol in the step (1) and uniformly stirring to obtain the anhydrous modified glycerol-based cross-linking fracturing fluid system.
And (3) performance testing:
the test is carried out by using a MAS-III high-temperature high-pressure rheometer: the fracture fluid is filled, the heating temperature of a rheometer is set, the shear stability of the fracture fluid system is determined by the change trend of apparent viscosity along with time, and the measured rheological property curve of the anhydrous fracture fluid system in example 1 is shown in figure 1 and is 170s at 144 DEG C-1The viscosity is maintained above 300 mPas after shearing for 1 h.
Example 2
The anhydrous modified glycerol-based cross-linking fracturing fluid system comprises the following preparation raw materials in percentage by mass: 7.5 parts by mass of 2-acrylamide-2-methylpropanesulfonic acid, 45 parts by mass of acryloyloxyethyl trimethyl ammonium chloride, 20 parts by mass of dimethyldiallylammonium chloride, 3.5 parts by mass of hydroxy acrylate (4-hydroxybutyl acrylate and hydroxypropyl acrylate), 10 parts by mass of acrylamide, 47.5 parts by mass of mixed alcohol (the mass ratio of glycerol, ethylene glycol and 1, 4-butanediol is 57.5: 27.5: 15), 29.2 parts by mass of 3# white oil, 3.1 parts by mass of span oil (span 80), 0.011 part by mass of catalysts (potassium persulfate, azobisisobutyronitrile and azobisisobutyroline hydrochloride), 3.0 parts by mass of reverse demulsifier (emulsifier NP-9), and 1.4 parts by mass of crosslinking agents (zirconium isopropoxide, zirconium citrate, zirconium formate, aluminum acetate, aluminum citrate and aluminum formate). The preparation method comprises the following steps:
(1) carrying out first mixing on glycerol, ethylene glycol and 1, 4-butanediol to obtain mixed alcohol;
(2) 2-acrylamide-2-methylpropanesulfonic acid, acryloyloxyethyltrimethyl ammonium chloride, dimethyldiallylammonium chloride, hydroxyl acrylate and acrylamide are subjected to second mixing and are uniformly stirred to form a solution A;
mixing the white oil and the span oil for the third time, and stirring uniformly to form a solution B;
pouring the solution A into the solution B for fourth mixing, and uniformly stirring to obtain a pre-emulsion; under the protection of nitrogen, adding a catalyst into the pre-emulsion, and simultaneously starting an emulsification pump to emulsify and homogenize to obtain an emulsion; slowly heating the emulsion to 90 +/-3 ℃, continuously reacting and curing for 4.5h, stopping heating, cooling the obtained reaction liquid to room temperature by using cold water at the temperature of-12 +/-3 ℃, adding a reverse demulsifier, and uniformly stirring to obtain a fracturing fluid thickening agent;
(3) and (3) adding the fracturing fluid thickening agent and the cross-linking agent in the step (2) into the mixed alcohol in the step (1) and uniformly stirring to obtain the anhydrous modified glycerol-based cross-linking fracturing fluid system.
The performance test of the anhydrous modified glycerol-based cross-linked fracturing fluid system in example 2 is carried out by the method in example 1, and the measured rheological performance curve of the anhydrous fracturing fluid system in example 1 is shown in FIG. 2, and is 170s at 145-148 ℃ in 170s-1The viscosity is kept above 250 mPas after shearing for 1 h.
The embodiment shows that the fracturing fluid provided by the invention is a waterless system, so that the fracturing fluid can be used for high-water-sensitive stratums, and the use of water resources and the pollution of flowback fluid are greatly reduced; the anhydrous modified glycerol-based cross-linked fracturing fluid system provided by the invention has excellent high-temperature resistance, and can well meet the industrial application of drilling and exploitation of high-water-sensitivity stratum oil and gas wells.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The anhydrous modified glycerol-based cross-linked fracturing fluid system is characterized by comprising the following preparation raw materials in parts by mass:
the mixed alcohol comprises glycerol, ethylene glycol and 1, 4-butanediol, and the mass ratio of the glycerol to the ethylene glycol to the 1, 4-butanediol is 50-60: 20-30: 10-20; the catalyst is potassium persulfate and/or azo catalyst; the cross-linking agent is an organic zirconium cross-linking agent and/or an organic aluminum cross-linking agent.
2. The anhydrous modified glycerol-based cross-linked fracturing fluid system of claim 1, which is characterized by comprising the following raw materials in percentage by mass:
3. the non-aqueous modified glycerol-based crosslinked fracturing fluid system of claim 1 or 2, wherein the hydroxy acrylate is 4-hydroxybutyl acrylate and/or hydroxypropyl acrylate.
4. The anhydrous modified glycerol-based crosslinked fracturing fluid system of claim 1 or 2, wherein the azo-based catalyst is azobisisobutyronitrile and/or azobisisobutyrimidazoline hydrochloride; the organic zirconium cross-linking agent is one or more of zirconium isopropoxide, zirconium citrate and zirconium formate; the organic aluminum cross-linking agent is one or more of aluminum acetate, aluminum citrate and aluminum formate.
5. The anhydrous modified glycerol-based crosslinked fracturing fluid system of claim 1 or 2, wherein the reverse demulsifier is emulsifier NP-8 and/or emulsifier NP-9.
6. The anhydrous modified glycerol-based crosslinked fracturing fluid system of claim 1 or 2, wherein the white oil is D-100 white oil and/or # 3 white oil; the span oil is one or more of span 20, span 40 and span 80.
7. The preparation method of the anhydrous modified glycerol-based cross-linked fracturing fluid system of any one of claims 1 to 6, characterized by comprising the following steps:
(1) carrying out first mixing on glycerol, ethylene glycol and 1, 4-butanediol to obtain mixed alcohol;
(2) carrying out second mixing on 2-acrylamide-2-methylpropanesulfonic acid, acryloyloxyethyltrimethyl ammonium chloride, dimethyldiallylammonium chloride, hydroxyl acrylate and acrylamide to obtain a solution A;
carrying out third mixing on the white oil and the span oil to obtain a solution B;
adding the solution A into the solution B for fourth mixing to obtain a pre-emulsion; under the protection of nitrogen, mixing the pre-emulsion with a catalyst for emulsification and homogenization to obtain an emulsion;
heating the emulsion to 87-93 ℃ for polymerization reaction, cooling the obtained reaction liquid to room temperature, and mixing the reaction liquid with a reverse demulsifier to obtain a fracturing fluid thickening agent;
(3) and mixing the mixed alcohol, the fracturing fluid thickening agent and the cross-linking agent to obtain the anhydrous modified glycerol-based cross-linking fracturing fluid system.
8. The preparation method according to claim 7, wherein the polymerization reaction time in the step (2) is 4.5 to 5 hours.
9. The production method according to claim 7 or 8, wherein the cooling in the step (2) is performed using cooling water having a temperature of-15 ℃ to-9 ℃.
10. The application of the anhydrous modified glycerol-based cross-linked fracturing fluid system of any one of claims 1 to 6 or the anhydrous modified glycerol-based cross-linked fracturing fluid system prepared by the preparation method of any one of claims 7 to 9 in the field of oil and gas exploitation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698541A (en) * | 2021-08-30 | 2021-11-26 | 大庆长垣能源科技有限公司 | Preparation method of low-temperature gel breaking alcohol-based anti-swelling fracturing system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492414A (en) * | 2011-12-05 | 2012-06-13 | 北京希涛技术开发有限公司 | Synthesis of thickening agent for methanol-based fracturing fluid |
| CN107793529A (en) * | 2016-09-05 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of high temperature resistant acid fracturing polymer and preparation method |
| CN109971454A (en) * | 2019-05-10 | 2019-07-05 | 四川洁能锐思石油技术有限公司 | A kind of instant crosslinked fracturing fluid system of modified ethylene glycol and its preparation method and application |
| CN110563865A (en) * | 2019-09-05 | 2019-12-13 | 江苏富淼科技股份有限公司 | High molecular weight low-residual-monomer polyacrylamide inverse emulsion and preparation method thereof |
| CN111574989A (en) * | 2020-05-28 | 2020-08-25 | 北京九恒质信能源技术有限公司 | Polyhydroxy thickening agent, high-temperature-resistant alcohol-based fracturing liquid system and application thereof |
-
2020
- 2020-11-27 CN CN202011354151.9A patent/CN112442352B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492414A (en) * | 2011-12-05 | 2012-06-13 | 北京希涛技术开发有限公司 | Synthesis of thickening agent for methanol-based fracturing fluid |
| CN107793529A (en) * | 2016-09-05 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of high temperature resistant acid fracturing polymer and preparation method |
| CN109971454A (en) * | 2019-05-10 | 2019-07-05 | 四川洁能锐思石油技术有限公司 | A kind of instant crosslinked fracturing fluid system of modified ethylene glycol and its preparation method and application |
| CN110563865A (en) * | 2019-09-05 | 2019-12-13 | 江苏富淼科技股份有限公司 | High molecular weight low-residual-monomer polyacrylamide inverse emulsion and preparation method thereof |
| CN111574989A (en) * | 2020-05-28 | 2020-08-25 | 北京九恒质信能源技术有限公司 | Polyhydroxy thickening agent, high-temperature-resistant alcohol-based fracturing liquid system and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698541A (en) * | 2021-08-30 | 2021-11-26 | 大庆长垣能源科技有限公司 | Preparation method of low-temperature gel breaking alcohol-based anti-swelling fracturing system |
| CN113698541B (en) * | 2021-08-30 | 2022-04-29 | 大庆长垣能源科技有限公司 | Preparation method of low-temperature gel breaking alcohol-based anti-swelling fracturing system |
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